Patent GB-1095288-A (GB)
Title: Polymer dispersions
Inventor: THOMPSON MORICE WILLIAM
IPC: C08J3/11
Filed: 1963-08-01
Abstract: A dispersion in organic liquid of crosslinkable addition polymers contains one polymer containing a reactive group which is capable of reacting with a complementary reactive group in another of the polymers to crosslink the polymers, each polymer being in a different part of the disperse phase.  In one embodiment, the dispersion contains a mixture of two types of dispersed polymer particles, in which the reactive groups may be confined to the inner layers of the particles.  In another embodiment, a monomer containing a first reactive group is polymerized in dispersion in an initial stage and a monomer containing a complementary reactive group is polymerized in a later stage to form particles containing reactive groups in different layers.  The polymerization is carried out in the presence of a stabilizer which may be formed in situ by copolymerizing the monomer with a polymeric precursor to form a block or graft copolymer. Pigments may be incorporated in the dispersion prior to removal of the organic liquid, the resulting dry polymer particles being cross-linked by fusion or dispersed in a plasticizer, e.g. a phthalate ester to form a plastisol, in which crosslinking occurs on heating and gelling.  In the first stage of Example 1, methyl methacrylate and methacrylic acid are copolymerized in petroleum ether using azodiisobutyronitrile as catalyst in the presence of poly (lauryl methacrylate-glycidyl methacrylate) as stabilizer precursor, in the second stage butyl methacrylate, methyl methacrylate and methacrylic acid are copolymerized in the dispersion from the first stage and in the third stage butyl methacrylate, methyl methacrylate and butoxymethyl acrylamide are copolymerized.  Octyl meraptan is present as molecular weight regulator.  In Example 2, a two-stage process is employed, the monomers being (1) methyl methacrylate and (2) methyl methacrylate and methacrylic acid and the resulting dispersion is mixed with a similar one in which butoxymethyl acrylamide replaces the methacrylic acid.  The monomers employed in Example 3 are (1) vinyl acetate, (2) vinyl acetate and methyl hydrogen maleate and (3) vinyl acetate and butoxymethyl acrylamide. In Example 7 the monomers are (1) methyl methacrylate and 2-hydroxypropyl methacrylate, (2) butyl methacrylate, methyl methacrylate and the reaction product of 2-hydroxypropyl methacrylate and toluene diisocyanate and (3) butyl methacrylate, 2-hydroxypropyl methacrylate and methyl methacrylate, in Example 8 the butyl methacrylate is omitted from stages (2) and (3) and in Example 9 the monomers are (1) methyl methacrylate and the methyl isobutyl ketimine of aminoethyl methacrylate, (2) butyl methacrylate, methyl methacrylate and methacrylyl chloride and (3) methyl methacrylate, butyl methacrylate and the said ketimine. Glycidyl methacrylate is used in Example 10 in place of the methacyl chloride in Example 9. In Example 11 the dispersion from Example 7 is mixed with a similar dispersion in which 2-hydroxypropyl methacrylate is used in place of the toluene diisocyanate adduct in stage (2) and in Example 12 the reaction product of cyanuric chloride and 2-hyroxyethyl methacrylate replaces the said adduct of Example 7.  Example 13 is similar to Example 3, the monomers used being (1) vinyl acetate, a hydroxyethyl acrylate/ toluene diisocyanate adduct and dibutyl maleate, (2) vinyl acetate and dibutyl maleate and (3) vinyl acetate, hydroxyethyl acrylate and dibutyl maleate.  The stabilizer precursor used in Examples 4 to 6 is alkylated polylauryl methacrylate, the catalyst is peroxy isopropyl dicarbonate and the monomers in Example 4 are (1) vinyl chloride and butoxymethyl acrylamide and (2) methyl hydrogen maleate; in Example 5 they are (1) vinyl chloride and methyl hydrogen maleate and (2) butoxymethyl acrylamide and in Example 6 butoxymethyl methacrylamide replaces the corresponding acrylamide used in Examples 4 and 5.